HEAT-STABILIZED AQUEOUS COMPOSITION

Abstract

A preparation of an aqueous composition that is resistant to temperature variations may include the use of at least one specific heat-stabilizing agent. The heat stabilization of the viscosity of the aqueous composition within a wide temperature range. Such heat-stabilizing agents may include, in polymerized form: (a1) an anionic monomer comprising a polymerizable olefinic unsaturation and a carboxylic acid group, optionally in salt form; (a2) a C1-C7 ester of acrylic acid, methacrylic acid, maleic acid, and/or itaconic acid; (a3) an associative monomer of a formula, R.sup.1-(EO).sub.m-(PO).sub.n-R.sup.2, wherein m and n are independently 0 or an integer or decimal less than 150, m or n being different from 0, EO is independently a CH.sub.2CH.sub.2O group, PO is independently a combination of (i) CH.sub.2CH.sub.2O and (ii) CH(CH.sub.3)CH.sub.2O and/or CH.sub.2CH(CH.sub.3)O, R.sup.1 is independently a group comprising a polymerizable olefinic unsaturation, and R.sup.2 is independently a straight C.sub.28-C.sub.40-alkyl group or a C.sub.28-C.sub.40-alkyl group.

Claims

1. A method for preparing an aqueous composition that is heat-resistant to temperature variations, the method comprising: adding at least one heat-stabilizing agent (P) comprising, in polymerized form: (a1) an anionic monomer comprising a polymerizable olefinic unsaturation and a carboxylic acid group, optionally in salt form; (a2) a C1-C7 ester of acrylic acid, methacrylic acid, maleic acid, and/or itaconic acid; (a3) an associative monomer of formula (I):
R.sup.1-(EO).sub.m-(PO).sub.n-R.sup.2   (I), wherein: m and n are independently 0 or an integer or decimal less than 150, m or n being different from 0, EO is independently a CH.sub.2CH.sub.2O group, PO is independently a combination of (i) CH.sub.2CH.sub.2O and (ii) CH(CH.sub.3)CH.sub.2O and/or CH.sub.2CH(CH.sub.3)O, R.sup.1 is independently a group comprising a polymerizable olefinic unsaturation, and R.sup.2 is independently a straight C.sub.28-C.sub.40-alkyl group or a C.sub.28-C.sub.40-alkyl group.

2. The method of claim 1 wherein the aqueous composition is a hydraulic binder composition, an adhesive composition, a detergent composition, a cosmetic composition, an ink composition, an aqueous paper coating composition, or a coating composition.

3. The method of claim 1, wherein: the monomer (a1) is acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt, or a combination thereof, or the monomer (a2) is a C.sub.1-C.sub.6 ester, or the monomer (a3) is a compound of formula (I) wherein: m and n are independently 0 or an integer or decimal less than 150, EO is independently a CH.sub.2CH.sub.2O group, PO is independently a combination of (i) CH.sub.2CH.sub.2O and (ii) CH(CH.sub.3)CH.sub.2O and/or CH.sub.2CH(CH.sub.3)O, R.sup.1 is independently an acrylate group or a methacrylate group, and R.sup.2 is independently a straight C.sub.32-C.sub.40-alkyl group, a branched C.sub.32-C.sub.40-alkyl group, a straight C.sub.30-C.sub.36-alkyl group, or a branched C.sub.30-C.sub.36-alkyl group.

4. The method of claim 1, wherein a polymerization reaction for the heat-stabilizing agent (P) uses, relative to total monomer weight: the monomer (a1) in a range of from 20 to 55 wt. %, the monomer (a2) in a range of from 20 to 79.5 wt. %, and the monomer (a3) in a range of from 0.5 to 25 wt. %.

5. The method of claim 1, wherein the heat-stabilizing agent (P) is prepared polymerizing: (a4) 2 acrylamido-2-methylpropane sulphonic acid, ethoxymethacrylate sulphonic acid, sodium methallyl sulphonate, styrene sulphonate, hydroxyethyl acrylate phosphate, hydroxypropyl acrylate phosphate, hydroxyethylhexyl acrylate phosphate, hydroxyethyl methacrylate phosphate, hydroxypropyl methacrylate phosphate, hydroxyethylhexyl methacrylate phosphate, or a combination thereof, optionally in salt form, (a5) hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethylhexyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethylhexyl methacrylate, or a combination thereof, (a6) at least one cross-linking monomer or at least one monomer comprising at least two olefinic unsaturations, (a7) at least one chain transfer agent.

6. The method of claim 1 wherein the heat-stabilizing agent (P) is at least partially neutralized, or is partially coacervated.

7. The method of claim 1, wherein the aqueous composition comprises from 0.05 to 5 wt. % of the heat-stabilizing agent (P), relative to total aqueous composition weight.

8. The method of claim 1, wherein the aqueous composition has a viscosity: measured for a shear gradient in a range of from 0.1 to 1,000 s.sup.−1 and for a temperature change in a range of from 5 to 50° C., in a range of from 50 to 98%, of the initial viscosity value of the aqueous composition, or measured for a shear gradient in a range of from 0.1 to 100 s.sup.−1 and for a temperature change in a range of from 5 to 50° C., in a range of from 50 to 98%, of the initial viscosity value of the aqueous composition or measured for a shear gradient in a range of from 1 to 100 s.sup.−1 and for a temperature change in a range of from 5 to 50° C., in a range of from 50 to 98%, of the initial viscosity value of the aqueous composition or measured for a shear gradient in a range of from 0.1 to 1 s.sup.−1 and for a temperature change in a range of from 5 to 50° C., in a range of from 55 to 98%, of the initial viscosity value of the aqueous composition.

9. A method of heat stabilizing viscosity of an aqueous composition, the method comprising: adding at least one of the heat-stabilizing agent (P) of claim 1 to the aqueous composition, wherein a decrease in viscosity measured for a shear gradient in a range of from 0.1 to 1,000 s.sup.−1 is less than 45%, for a temperature range in a range of from 5 to 50° C., relative to an initial viscosity of the aqueous composition, or wherein a decrease in viscosity measured for a shear gradient in a range of from 0.1 to 100 s.sup.−1 is less than 50%, for a temperature range in a range of from 5 to 50° C., relative to the initial viscosity of the aqueous composition, or wherein the decrease in viscosity measured for a shear gradient in a range of from 1 to 100 s.sup.−1 is less than 50%, for a temperature range in a range of from 5 to 50° C., relative to the initial viscosity of the aqueous composition, or wherein a decrease in viscosity measured for a shear gradient in a range of from 0.1 to 1 s.sup.−1 is less than 50%, for a temperature range in a range of from 5 to 50° C., relative to the initial viscosity of the aqueous composition.

10. The method of claim 9, wherein the heat-stabilizing agent (P) is added in a range of from 0.05 to 5 wt. % to the aqueous composition, relative to total aqueous composition weight.

11. A method for improving resistance to temperature changes of an aqueous composition, the method comprising: adding at least one of the heat-stabilizing agent (P) of claim 1 to the aqueous composition.

12. The method of claim 1, wherein the aqueous composition is a varnish composition.

13. The method of claim 1 wherein the aqueous composition is a paint composition.

14. The method of claim 1, wherein the monomer (a1) is acrylic acid, methacrylic acid, an acrylic acid salt, and/or a methacrylic acid salt.

15. The method of claim 1, wherein the monomer (a2) is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethyl hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl hexyl methacrylate, or a combination thereof.

16. The method of claim 1, wherein the monomer (a2) is ethyl acrylate, butyl acrylate, methyl methacrylate, or a combination thereof.

17. The method of claim 3, wherein, in the monomer (a3), R.sup.2 is independently a straight C.sub.32-C.sub.36-alkyl group or a branched C.sub.32-C.sub.36-alkyl group; more preferentially a branched C.sub.32-alkyl group.

18. The method of claim 1, wherein a polymerization reaction for the heat-stabilizing agent (P) uses, relative to total monomer weight, the monomer (a1) in a range of from 25 to 45 wt. %, the monomer (a2) in a range of from 35 to 74 wt. %, and the monomer (a3) in a range of from 1 to 20 wt. %.

Description

EXAMPLES

Example 1

Preparation of a Compound (P1) According to the Invention and of a Comparative Compound (CP1)

[0120] In a 3 L glass reactor (container 1) equipped with a mechanical stirring, vacuum pump, and nitrogen inlet and heated by means of a double jacket in which oil circulates, 890 g of bi-permuted water is introduced and heated to 75° C. in an inert atmosphere. 10.5 g of sodium dodecyl sulphate powder is then added and the medium is stirred until completely dissolved. In a 1,000 mL glass beaker (container 2) equipped with magnetic stirring, the following are successively added: 338 g of bi-permuted water, 3.4 g of sodium dodecyl sulphate powder which is stirred until completely dissolved, 317 g of ethyl acrylate, 186.2 g of methacrylic acid and 19.5 g of ethoxylated dotriacontane alcohol methacrylate (monoalcohol comprising a branched C.sub.32-alkyl group) with 25 ethylene oxide equivalents (compound (a3) of formula (I) wherein R.sup.1 represents a methacrylate group, m represents 25, EO represents an ethylene-oxy group, R.sup.2 represents a branched C.sub.32-alkyl group). This mixture is stirred for 15 minutes to ensure good homogenisation. Then, 1.83 g of ammonium persulphate and 0.183 g of sodium metabisulphite are quickly added to container 1. Then, the contents of container 2 are injected into container 1 with a peristaltic pump over 120 minutes. After 2 hours of reaction, the temperature is increased to 80° C. for 30 minutes. The appropriate amount of water is then added to bring the solids content to 30% by mass. An aqueous emulsion of the heat-stabilising agent (P1) according to the invention is obtained.

[0121] Similarly, a comparative compound (CP1) is prepared. In a 3 L glass reactor (container 1) equipped with a mechanical stirring, vacuum pump, and nitrogen inlet and heated by means of a double jacket in which oil circulates, 920 g of bi-permuted water is introduced and heated to 75° C. in an inert atmosphere. 12.9 g of sodium dodecyl sulphate powder is then added and the medium is stirred until completely dissolved.

[0122] In a 1,000 mL glass beaker (container 2) equipped with magnetic stirring, the following are successively added: 321 g of bi-permuted water, 4.5 g of sodium dodecyl sulphate which is stirred until completely dissolved, 311.5 g of ethyl acrylate, 180 g of methacrylic acid and 27.2 g of ethoxylated behenyl alcohol methacrylate with 25 equivalents of ethylene oxide. This mixture is stirred for 15 minutes to ensure proper homogenisation. Then, 1.8 g of ammonium persulphate and 0.18 g of sodium metabisulphite are quickly added to container 1. Then, the contents of container 2 are injected into container 1 with a peristaltic pump over 120 minutes. After 2 hours of reaction, the temperature is increased to 80° C. for 30 minutes. An aqueous emulsion of a comparative compound (CP1) is obtained.

Example 2

Preparation and Evaluation of Aqueous Formulations Comprising a Heat-Stabilising Agent (P1) According to the Invention or a Comparative Compound (CP1)

[0123] 6.7 g of aqueous emulsion of heat-stabilising agent (P1) in example 1 is weighed in a 500 mL glass beaker. 393.3 g of bi-permuted water is then added in order to obtain 400 g of aqueous solution of heat-stabilising agent (P1). This solution is placed under vigorous mechanical stirring. Then, its pH is brought to 8+/−1 by adding an aqueous sodium hydroxide solution at 50% by mass. Stirring is continued for 2 minutes, then the gel is left to rest for 24 hours.

[0124] Similarly, a comparative formulation CF1 comprising a comparative compound (CP1) is prepared instead of the agent (P1).

[0125] 8 g of aqueous emulsion of comparative compound (CP1) in example 1 is weighed in a 500 mL glass beaker. 392 g of bi-permuted water are then added in order to obtain 400 g of aqueous solution of compound (CP1). This solution is placed under vigorous mechanical stirring. Then, its pH is brought to 8+/−1 by adding an aqueous sodium hydroxide solution at 50% by mass. Stirring is continued for 2 minutes, then the gel is left to rest for 24 hours. The amount of water in the formulation CF1 can be adjusted so that this formulation has a starting viscosity comparable to that of the formulation F1.

[0126] The thickening efficacy of the formulations is assessed after 24 hours by measuring flow curves for various shear gradients (Thermo Scientific Mars III rheometer using a cone-planar geometry of 60 mm in diameter with a 1° angle) and at different temperatures.

[0127] The heat stability of the formulation is then assessed by calculating the change in viscosity depending on the temperature change for the various shear gradients applied. The change in viscosity is calculated in a standardized manner relative to the viscosity measured at 4.9° C. For each viscosity value measured, the ratio R (viscosity measured at a certain temperature/viscosity measured at 4.9° C.) corresponding to the residual viscosity of each formulation assessed, is calculated.

[0128] The results of the viscosity values and R ratios for the formulation F1 comprising the agent (P1) according to the invention are shown in Table 1.

TABLE-US-00001 Formulation F1 comprising the agent (P1) Viscosity (mPa .Math. s) Temperature per shear gradient (s.sup.−1) (° C.) 0.1 1 100 4.9 189.80 23.52 0.46 10.0 184.50 21.98 0.43 14.9 180.30 20.80 0.41 20.0 168.70 19.48 0.38 24.9 159.80 18.84 0.36 29.9 152.00 18.26 0.34 35.0 138.20 17.44 0.32 39.9 131.20 16.91 0.30 45.1 122.50 16.07 0.28 50.0 118.30 15.34 0.27 R Temperature per shear gradient (s.sup.−1) (° C.) 0.1 1 100 4.9 1.00 1.00 1.00 10.0 0.97 0.93 0.93 14.9 0.95 0.88 0.88 20.0 0.89 0.83 0.82 24.9 0.84 0.80 0.78 29.9 0.80 0.78 0.75 35.0 0.73 0.74 0.70 39.9 0.69 0.72 0.66 45.1 0.65 0.68 0.61 50.0 0.62 0.65 0.58

[0129] The results of the viscosity values and R ratios for the comparative formulation CF1 comprising the comparative polymer (CP1) are shown in Table 2.

TABLE-US-00002 Formulation CF1 comprising the agent (CPI) Viscosity (mPa .Math. s) Temperature per shear gradient (s.sup.−1) (° C.) 0.1 1 100  4.9 20.30 15.20 16.20 10.0 18.27 14.04 14.39 14.9 16.74 13.02 13.31 20.0 12.82 10.80 11.06 24.9 9.91 9.08 9.25 29.9 7.20 7.25 7.35 35.0 4.05 4.59 4.63 39.9 2.61 3.08 3.10 45.1 1.29 1.48 1.47 50.0 0.79 0.86 0.85 R Temperature per shear gradient (s.sup.−1) (° C.) 0.1 1 100  4.9 1.00 1.00 1.00 10.0 0.90 0.92 0.89 14.9 0.82 0.86 0.82 20.0 0.63 0.71 0.68 24.9 0.49 0.60 0.57 29.9 0.35 0.48 0.45 35.0 0.20 0.30 0.29 39.9 0.13 0.20 0.19 45.1 0.06 0.10 0.09 50.0 0.04 0.06 0.05

[0130] For different shear gradients, the change in viscosity of the formulations comprising an agent (P1) according to the invention or a comparative polymer (CP1) is compared for various temperature ranges by calculating the viscosity loss. The viscosity loss results are shown in Table 3.

TABLE-US-00003 Temperature Viscosity loss (%) per range shear gradient (s.sup.−1) Formulation (° C.) 0.1 1 100 with (P1)  5->15 5 12 12 15->35 23 16 21 30->50 22 16 22  5->50 38 35 45 with (CP1) 0.1 1 100  5->15 18 14 18 15->35 76 65 65 30->50 89 22 88  5->50 96 94 95

[0131] For many temperature ranges, it is possible to observe that the heat-stabilising agents according to the invention make it possible to limit the viscosity loss much more significantly than the comparative polymer. This viscosity stabilisation is possible for shear gradients corresponding to many conditions of use or application of aqueous compositions.